Phthalocyanine dyestuffs containing halo-pyrimidyl groups



United States Patent Office 3,l05,'0=70 Patented Sept. 24, 1963 PHTHALOCYANINE DYESTUFFS CONTAINING HALO-PER GRQUPS Peter Bitterli, Basel, Switzerland, assignor t9 Sandoz Ltd.,

Basel, Switzerland, :1 Swiss firm No Drawing. Filed Mar. 26, 1962, Ser. No. 182,610 Claims priority, application Switzerland Apr. 12, 1960 7 Claims. (Ci. 260-242) This application is a continuation-in-part of application Ser. No. 100,002, filed April 3, 19 61 (abandoned since the filing of the present application), and relates to dyes of the phthalocyanine series which contain reactive groups and have the formula wherein PC represents a metal-free or metal-containing phthalocyam'ne radical which may be further substituted by one or two chlorine or bromine atoms,

A represents a low molecular alkylene radical which may be further substituted, each of A and A represents a phenylene or low molecular alkylene radical which may be further substituted, A and A being different from each other,

R represents a dior trihalogenopyrimidyl radical wherein Hal stands for chlorine or bromine,

R represents hydrogen or a low molecular alkyl radical,

n possesses a value of at least 2 but not more than 4, in the absence of phenylene radicals and at least 3 but not more than 4 in the presence of a phenylene radical, and

m, x, y and z each possesses a value of at least 1 but not more than 4, the total x+y+z being 6 and the -SO H and R2 groups being attached to the radicals A A and A Particularly interesting dyes are those in which PC represents an unsubstituted metal-free phthalocyanine radical or an unsubstituted copper or nickel phthalocyanine radical or a copper phthalocyanine radical bearing one or two chlorine or bromine atoms.

The process for the production of the new dyes consists in reducing the sulfonic acid halide groups in phthalocyanine-tetrasulfonic acid halides of the formula PC(SO Hal) (11) wherein PC and Hal possess the aforecited meanings, and reacting the resulting polythiol with one or more alkylating agents or a mixture of phenyla-ting and alkylating agents which contain sulfonic acid groups and/ or -NHR groups or D substituents convertible into these groups and further substituents if desired, so that the alkylthioethers or the phenyland alkylthioethers obtained possess at least m NHR or D groups and at least two sulfonic acid groups, converting the D substituents when present into the NHR -'group or groups, and condensing 1 mole of the amino dyestufi or the mixture of amino dyestuffs with m moles of a trior tetrahalogenopyrimidine, wherein Hal stands for chlorine or bromine.

The phthalocyanine-tetrasulfonic acid halies of Formula II are reduced to the corresponding thiol compounds preferably in acid medium, e.g., in hydrochloric and/or sulfuric acid-aqueous medium, in presence of iron or zinc. The thiol compounds thus formed are reacted with the alkylating agents or mixtures of phenylating and alkylating agents preferably in aqueous alkaline medium at pH value of 814 and at temperatures between 20-100 C., preferably 60-90 C., with the addition of an acid-binding agent, e.g. sodium hydroxide, carbonate or bicarbonate, or the corresponding potassium salts.

If the phenylating and/or alkylating agents contain D substituents convertible into the group -NHR e.g. one to two nitro groups in the phenylating agents or a group acyl-N-R at least one nitro group is to be reduced, e.g. by heating with an aqueous solution of sodium sulfide or sodium hydrogen sulfide, preferably at temperatures of 60 to C. or with iron powder or filings in a dilute mineral acid, preferably in 5 to 10% hydrochloric :or sulfuric acid, at 0 to C., preferably at 20-80" C., or with a mixture of stannous chloride and concentrated hydrochloric acid, e.g. a-t 50l0 0 C., or the group acyl-N-R is to be hydrolyzed, e.g. by heating in an aqueous alkali metal hydroxide solution, preferably in 5 to 10% sodium or potassium hydroxide solution, at 70 to 100 C. or in a dilute mineral acid, preferably in 5 to 10% hydrochloric :or sulfuric acid at 70 to 100 C.

Examples of suitable phthalocyanines are the metal-free phthalocyanine, copper and nickel phthalocyanines, monoor dichloroor monoor dibromo-copper phthalocyanines.

The following are examples of phenylating or alkylating agents suitable for reaction with the thiol: l-chloro-4- ni-trobenzene, l chloro-2-nitrobenzene-4 sulfonic acid, 1- chloro-4 nitrobenzene 2 sulfonic acid, 1,2-dichloro-4- nitrobenzene-S-sulfonic acid, l-chloro-2,4-dinitrobenzene- 6-sulfonic acid, B-chloroethanesulfonic acid, the inner anhydride of fi-sulfonyl-oxyethanesulfonic acid (carbyl sulfate"), fl-[( 4 methyl) phenylsulfonyloxy]-ethanesulfonic acid, B-chloro-2-hydroxypropane-l-sulfonic acid, 4-methylsulfonyloxybutane-l-sulfonic acid, 2chloroethylamine, acetic acid N-(2-chloro)-ethylamide, N-(2- chloroethyl)N-methylamine, the sulfuric acid esters of fi-aminoethanol, l-amino-Z-propanol or 1-amino-3-butanol, 2-(2'-chloro-ethylamino)-ethane-1-sulfonic acid, 3- (2'-chloroethylamino) -2-hydroxypropane-l-sulfonic acid.

Triand tetrahalogenopyrimidines which may be condensed with the -NHR group or groups are e.g.: 2,4,6- tri-chloropy-rimidine and 2,4,6-tribromopyrimidine, and their derivatives which may contain, for example, the following substituents in the 5-position: methyl, ethyl, carboxylic acid, carboxylic acid methyl or ethyl ester, ,alkenyl, e.g. allyl, chlorovinyl, substituted alkyl, e.g. carboxymethyl, chloromethyl or bromomethyl, 2,4,5,6-tetrachloroor -tetrabromopyrimidine, 2,4,5-tiichloropyrimidine, 2,4,5-tribromopyrimidine, 2,5,6-t-richloro-4-methylpyrimidine, 2,5,6-tribromo-4-methylpyrimidine, 2,4-diehloro-S-chloromethyl-6-methylpyrimidine, 2,4-dibromo- 5 -bromomethyl 6 methylpyrimidine, 2,4 dichloro-5- chloromethylpyrimidine, 2,4 dibromo 5 bromomethylpyrimidine and 2,6-dichlorol-trichloromethylpyrimidine.

The reaction is carried out preferably at temperatures of 40 .to 100 C. in a weakly alkaline, neutral to weakly acid medium, but preferably within the pH range of 9 to 3. To neutralize the hydrogen halide formed, an acidbinding agent, e.g. sodium acetate, is added to the solution at the start of the reaction, or small portions of sodium or potassium carbonate or bicarbonate in solid powder form or in concentrated aqueous solution are added during the course of the reaction. Aqueous solutions of sodium or potassium hydroxide are also suitable as neu tralizing agents. The addition of small amounts of a wetting or emulsifying agent to the reaction mixture can accelerate the rate of reaction.

Owing to the volatility in steam of certain halogenopyrimidines it is advisable to work in vessels fitted with reflux condensers. The reaction is so conducted that only :9 7 one halogen atom reacts with an exchangeable hydrogen atom.

The'condensation products are isolated from their aqueous or aqueous-organic solutions by evaporation or by salting out or acidification. They are then filtered off, washed, neutralized in paste form if desired, and finally dried.

The new dyestulfs are suitable for the dyeing of leather; for the dyeing, padding and printing of fibers of animal origin, e.g. wool, silk; synthetic polyamide fibers, e.g. nylon, Perlon (registered trademark); and in particular cellulosic fibers, e.g. cotton, linen, viscose rayon, viscose staple fiber and cuprammonium rayon; and also mixtures and other articles of these fibers.

The new dyestuffs possess good solubility in Water, good compatibility to salts and hard Water and good reactivity with vegetable fibers. In contrast to the corresponding tetra-(arylthio)-phthalocyanines they yield printing pastes and padding liquors stable to storage. They are insensitive to heavy metal ions such as copper, iron and chromium ions.

During or after dyeing or padding, or after printing on cellulosic fibers as the case may be, the goods are I submitted to heat treatments. The normally used Wetting,

levelling, thickening and other textile or leather auxiliary products can be used in dyeing, padding and printing with these dyestuffs. {The heat treatment is carried out in presence of alkali.

The addition of certain quaternizable amines such as trimethylamine, triethylenediamine. or of asymmetric 'dimethylhydrazine, preferably in stoichiometric amounts,

accelerates the fixation of the dyestulf on the fiber, so that the fixation temperature can be lowered and/ or the fixation time shortened.

Owing to the rather slight substantivity of the new dyestulfs, the unfixed dyestulf portion can easily be removed from the dyeings and prints on cellulosic fibers without staining the unprinted areas. 7

The green dyeings and prints obtained possess very good Wet fastness properties to perspiration, Water and sea water combined with good to very good fastness to light, alkali, organic acids, rubbing and dry cleaning.

They are stable to organic solvents. The dyestuffs of the invention reserve cellulose acetate and triacetate, polyacrylonitrile fibers, polyvinyl chloride and polyvinyl acetate fibers, linear aromatic polyester fibers and polyalkylene fibers. i I

In the following examples the parts and percentages are by Weight and the temperatures in degrees centigrade.

Example 1 by external cooling. Stirring in presence of nitrogen is continued for 16 hours at 20 and then for 2 hours at 80. The precipitated tetra-(3) mercaptophthalocyanine is filtered off with suction and washed with warm water until it is free of iron salts and of neutral reaction.

The moist thiol is suspended in 1200 parts of water in presence of nitrogen. After the addition of 68 parts of 30% sodium hydroxide solution, 40 parts of sodium 3-chloro-2-hydroxypropane-l-sulfonate and 55 parts of sodium 1-chloro-4-nitrobenzene-Z-sulfonate the reaction mass is stirred at 90 for 16 hours and nitrogen conducted through it during this time. The deep green solution is freed from undissolved matter by filtration.

Reduction is effected by adding 45 parts of sodium sulfide to the filtrate and stirring for 1 hour at 80, upon which concentrated hydrochloric acid is added until the solution react acid to Congo red indicator paper.

The precipitated dye is filtered oil and washed with 200 parts of 1% hydrochloric acid. The filtercake is stirred into 800 parts of water, brought into solution by the addition of sodium hydroxide solution at a pH value of 7-8, and freed from precipitated sulfur by filtration. The solution is heated to 7 080 and 22 parts of 2,4,5,6-tetrachloropyrimidine are added in portions; simultaneously su-fficientsodium hydroxide solution is dropped in to maintain a constmt pH of 67. When the reaction has run its course the dye is precipitated by acidification and salting out, filtered with suction, Washed neutral with 5% sodium chloride solution and dried in vacuum at 50. The dye obtained dissolves in concentrated sulfuric acid'to give gray-green solution and in water bright green solutions.

Unmercerized cotton fabric is printed with a printing paste of the following composition:

30 parts of the dye produced as described above parts of urea 395 parts of water 450 parts of a 3% sodium alginate thickening -10 parts of sodium l-nitrobenzene-S-sulfonate 15 parts of anhydrous sodium carbonate 1000 parts The printed fabric is dried, steamed for 10 minutes at 102104-, rinsed in cold and warm water, soaped at the boil, rinsed and dried. A bright green print of good light and Wet fastness is obtained.

When the sodium 3-chloro-2-hydroxypropane-l-sulfonate employed in Examplel is replaced by 34 parts of sodium Z-chloroethanesulfonate, a dye with similar properties is obtained. Analogously, sodium 1-chl0ro-4-nitrobenzene-Z-sulfonate can be replaced by the same amount of sodium 1-chloro-2-nitrobenzene-4-sulfonate or by 57 parts of sodium 1,Z-dichloro-4-nitrobenzene-fi sulfonate to give a dye slightly more yellowish in shade.

-When the tetra-3-mercapto-copper phthalocyanine is replaced by the same amount of tetra-3-mercapto-nickel phthalocyanine (obtained from nickel phthalocyanine by 7 sulfochlorination and reduction of the sulfonic acid chlo ride with iron and hydrochloric acid), a brilliant green dye with good wet fastness properties is obtained.

Example 2 The dye produced with tetra-3-mercapto-copper phthalocyanine (from 58 parts of copper phthalocyanine), 40 parts of sodium 3-chloro-2-hydroxypropane-l-sulfonate and 71 parts of sodium 1,2-dichloro-4-nitrobenzene-6- sulfonate by condensation and reduction according to the particulars of Example 1 is dissolved in 800 parts of water at 80-90 and reacted with 18.5 parts of 2,4,6-trichloropyriniidine. The liberated hydrochloric acid is neutralized by the gradual addition of about 40 parts of 10% sodium hydroxide solution, which maintains the pH value of the solution at 6-7. The product is a dye having similar properties to that of Example 1 but giving a more yellowish green shade.

A padding solution is prepared with 10 parts of the above dye in 1000 parts of water and 10 parts of sodium carbonate. A cotton fabric is impregnated with this solution, passed between squeeze rollers so that it contains about 70% of its dry weight of liquor, and dried. The padded good is treated in dry heat'for about 5 minutes at rinsed with cold and warm water, soaped at the boil for 15 minutes with a 0.050.1% solution ofa nonionic detergent and rinsed. A green dyeing is obtained, which is fast to Washing, perspiration, Water, sea water, soda boiling, pressing, rubbing and dry cleaning.

Example 3 A solution is prepared with tetra-3-mercaptocopper phthalocyanine, produced from 58 parts ,of copper phthalocyanine by the procedure described in'Example 1, 600 parts of Water and 75 parts of 30% sodium hydroxide solution. At 60 40 parts of sodium 3-chloro-2- hydroxy-propane-l sulfonate are added in a nitrogen atmosphere. After stirring for 3 hours at 60, 28 parts of The ttetra-4-mercaptocopper phthalocyanine is obtained from copper phthalocyanine tetra-4-sulfonic acid by conversion into the sulfonic acid chloride and Subsequent reduction with iron and hydrochloric acid according to the 30% sodium hydroxide solution and 24 parts of 2-chloro- 5 details given in Example 1.

ethylamine chlorohydrate are added and stirring continued for 16 hours at 60. The undissolved components are re- Example 5 moved by filtration and the dye precipitated by adding to the warm solution 450 parts of 30% hydrochloric acid and sohlhon of 2 Parts of f y the form 0f the cooling to 20. It is filtered and Washed with 1000 Sodlum Salt) Ohialfled ficcordmfg to mp 1 from tetraparts f hydrochloric acid 3-meroaptocopper phthalocyanine, sodium 3-chloro-2 -hy- The intermediate product is dissolved in 800 parts of droxypropane 'l'sulfonate and sqdlum j Water and reacted with 22 parts f 2,4,5,6 tetrach1oro benzene-Z-sulfonate by condensation and reduction, are pyrimidine at 30 at a PH value of The dye is reacted with 3.6 parts of 2,4-dichloro-S-chloromethyl-6- lated by evaporating the solution. When 2-chloroethyl 1 methylplfnmldlhe 300 Parts of Water 3 P amine chlorohydrate is replaced by 26 parts of N-methyl- 1 bemg mamtalneq at about y the ad'dltlonfif N 2 ch1omethy1amine cmomhydrate, a green dye with sodium hydroxide solution. On completion of thereaction Similar properties is Obtained the dye is precipitated by acidification and salting out,

filtered off, washed with a sodium chloride solution and Example 4 V dried at 50 with vacuum.

20 parts f h d (i th form of h di lt) In the following table are listed further dyes of the obtained by the procedure of Example 1 f tet -4- Formula I which are obtainable according to the parmercapto-copper phthalocyanine, sodium 3-chloro-2- hyticulars of Examples 1 to 5 and are characterized by the droxypropane-l-sulfonate d odi 1 h1 -4 nitmten-amercaptophthalocyanme (obtained by reduction of benzene-Z-sulfonate by condensation and reduction, are the f p h Phthalocyahlhfi-tatfa'shlfomc acid dissolved in 300 parts of cold Water. The solution is 16- 6011mm 1, E116 p y h agent agents and Its t d ith 3 4 parts f 2,4,5,6 t t hl i jdi th or their amount in columns II and III, the alkylatmg agent reaction temperature being maintained at 75-80 and the or ag a HS amount 1n columns IV and the pH value of the solution at about 7 by the gradual addition phlyhalogehopyrlmldlhs and its -am0l111t In 111 VI of dilute sodium hydroxide solution. On completion of and VII and the Shade of {he dyelhg 011 cotton. 011 column the reaction any remaining unreacted 2,4,5,6-tetraehloro pyrimidine is filtered off, and the dye salted out of the The amounts in moles mentioned 111 columns HI, V and filtrate, filtered with suction and dried at with vacuum. VII refer to the one mole of tetramercapto-phthalocyanine.

Ex. Polymercapto- Shade of pad No. phthalocyanine Phenylating agent(s) Moles Alkylating agent(s) Moles Reactive system Moles dyeitng on Tetra-3-mercapto l-chloro--nitroben- 1 1 Green. 6 copper phthalocyazene. 2 chloro-ethane-l-sulfon- 2 2,4,5,6-tetra-ch1oronine. l-chloro-4-nitrobcnzine- 1 ie acid. pyrimidine S-sulionic acid. 7 1 d0 1-chloro-2,4-dinitro- 2 d0 2 d0 1 Do.

benlzene-fi-sulionic 3C1 8 do -do 1 4-methyl-sulfonyl-oxy- 3 2,4,6-trich1oro-pyri- 1 Do.

' butane-l-sulfonic acid. midine. 9 d0 l-chlor'oAmitroben- 1 Carbylsuliate 3 2,4 dichloro-fi chloro- 1 Do.

zene. methyI-Gqnethylpyrimidine. 10 do 1-chloro-4-nitroben- 2 2-[(4-methy1)-phcnyl- 2 do 2 Do.

zene-2-sulfonic acid. sulfonyloxyjl-ethancdsulionic acid. 11 .do do 1 3-chloro-2-hydroxypro- 3 2,4,6tribromo-pyrim- 1 Do.

' pane-l-sulionic acid. idine. 12 do do 2 do 2 2, 1,d5 -triehl0ro-pyrim- 1 Do.

l 1116. 13 do do 2 do 2 2,4,6-trichloro-5- 1 Do,

methylpyrimidine. 14 do do 2 d0 2 2,4.6-trichloro-5-car- 1 Do.

boxymethylpyrimidine. 15 do do 2 d0 2 2,4-dibr0mo-5-bromo 1 Do.

methyl-fi-methylpyrimidine. 16 do do- 2 do 2 2,4,5,6-tetrabromo- 1 Do,

pyrimidine. 17 Tetra-4 mercapto do 1 2-chloropr0pane-1-sul- 3 2,4,5,6-tetra-ch1oro- 1 Do,

copper phthaloionic acid. pyrimidine. cyanme. 18 do 1-chloro-2-nitroben- 2 -do 2 dn 1 Do.

zene--sulfonic acid. 19 Tetra-3-mercapto 1-cl1loro-4-nitr0ben- 1 do 3 2,4,6-trichloro-5 1 Bluish-green.

nickel phthalozene-2-suli0nic acid. ethylpyrimidine. cyanme. 20 d Ace ";1ic]acidd(2-chloro)- 2 St 111 e yarm e. 2,4, ric orc- 2-chloroethane-1- 2 pyrimidine. 2 Green sulionic acid. 2-grznigioethyl-sulfunc 2 24y5q -tqtr'achlow 1 21 -do 2-(2-chloro-cthyla- 2 Pynmldmemino)-ethane-1-sultonic acid. l-aminopropyl-2-sul 2 22 "do sulfuric acid. do 1 Green-blue.

2-brom0cthane-1-sul- 2 tonic acid. 23 do 1-chlor0-4-nitroben- 1.5 3-(2'-chloroethyla- 2.5 do 1.5 Do.

zene-2-sulfonic acid. mino)-2 hydroxy-propanc-l-sulionic acid. 24 do d 2 0 2 2,4,6-tribromo-5-car- 1 Do.

boxypyrimidine.

See footnotes at end of table.

See footnotes at end of table.

' Ex. Poiymercapto- Shade of pad No. phthalocyanine Phenylaiing agent (s) Moles Aikylating agent (s) Moles Reactive system Moles dyeitrgg on co on (I) (II) (III) (IV) (V) (VI) (VII) (VIII) 25 Tetra-3-mcrcapt0 1-ch1oro-4-nitrobon- 2 3-chlcro-2-hydroxy-pro- 2 2,4,5,6-tetrabromo- 1 Green.

copper phthalocyazene-2-su1fonic acid. pane-1-su1fonic acid. pyrimidine.

. nine.

26 .do 1,2dich1oro-4-nitro- 1.5 do 2.5 2,4,6-trich10r0-5-car- 1.5 Do.

benzene-fi-sulfonic boxmethyipyrimacid. idine.

27 .do d 2 2-chlorocthane-i-su1- 2 2,4-dibromo--bromo- 1 D0.

ionic acid. methy1-6-methy1- pyrimidine.

28 d0 d0 2 do 2 2,4,6-trichr0-5-car- 2 Blue-green.

bo yPY imidme. 3-chiorol-2-lililydroxy-pro- 2 t h] pane- 5 ionic acid. 2,4.6- ric oropyrimi- 29 1 2-(2-ch1crocthylamino)- 1 dine 1 ethane-l-sulfonic acid.

30 do l-chloro-4-nitrobon- 2 3-chior0-2-hydron'prd 2 2,4,6-tribr0In0-5-ethy1- 1 Green.

zene-2-suif0nic acid. pane-I-sulionic acid. pyrimidine.

31 do do 2 d0 2 2,e,6-tribromo-5- 1 Do.

bromomethylpyrimidine. 32 do do 2 2-ch1or0-ethanc-1-sui- 2 2.4-dichl0ro-5-chior0- 1 Do.

. ionic acid. mcthyI-G-methyipyrimidine. 33 d0 d0 2 d0 2 2,4.6-trich10ro-5- 1 Do.

chiorovinyL pyrimidine.

34 Mono-3-ci1i0rotetrado 2 do 2 2,4,6-trich1oropyrim- 1 Do.

3/6-mercapto copper idinc. phthalocyanine. I

35 Di-3-ch10rotetra-3/6- d0 1 d0 3 2,4,5,6-tetrachloro- 1 Do.

mercapto copper pyrimidine. phthalocyaninc.

36 Tetra3mercapto cop- 1,2-dich1oro-4mitro- 1. 5 do 2. 5 2,4.5-i3rich1010pyri1m 1. 5 D0.

per phthaiocyanine. benlzene-dsuifonic dine acrc 37 Tetra-d-mercapto copd0 1 d0 3 2,4-dich10r0-5-chioro- 1 D0.

pcr phthalocyanine. methylpyrimidine.

38 Di-3-bromo-tetra-3/6- IZ-chloro-ethyl-amine. 1 {2, 4, 5, G-tetra-chlcro- 1 D0 mercapto copper L2-ch1oro-ethanc-1- 3 pyrimidine.

sulionic acid. 2-(2-ch1oro-ethy1- 1 amino)-ethane-i- 39 M0n0-3-bromo-tetrasulfonic acid. do 1 Do B/FrmercaptO copper 3-ch1oro-2-hydroxy- 3 7 phthaiocyanine. propanc-l-suiionic J ac 40 do l-chioro i-ni- 1 3-ch1oro-2-hydr0xy- 3 2, 4, fi-trichioro- 1 Do.

trobenczcnc-2-su1- propane-l-sulfonic pyrimidine. ionic acid. acid.

41 Tetra-3-mercapto d0 1 do 3 2, 4, 6-tribromo-6- 1 D0.

copper phthalocyacarboethoxypyriminine. dine.

42 do do 1. 5 do 2. 5 '2, 4, 5, 6-tetra- 1.5 Do.

chime-pyrimidine.

43 do do 3 d0 1 d 3 Do.

44 do l-chioroi-nitro- 1 do 3 do 1 D0.

benzene. N (2 1 h 1) N Y 2 2 4 fitri 11100 45. do methylamine. 7 r r 2 1 2-chioroethane-1- 2 pymmdme suiionic acid. 7 2-aminoethy1-su1furic 1 46 do 1-ch1or0-4-nitrobcn- 2 acid. do 2 5 D zcne2-suif0nic acid. 2-ch1oroethane-l-su1- 1 ionic acid. 47 do 1-br0m0-4-nitrobcn- 2 3-chioro-2-hydroxy-pro- 2 2,4,6-trichlor5-5- 1.2 Do.

zene-Z-sulionic acid. pane-l-suiionic acid. carboxymethyl- 7 pyrimidine. 48 -do do 2 d0 2 2,5,6trich10r0-4- 7 1.4 Do.

' methyipyrimidine. 49 Tetra-4-rncrcapto l-chioroA-nitrdben- 1 2-ch1oro-ethanc-1-sul- 3 2,4,6-tribromo-5- 1 Do.

. copper phthalocyazene-Z-sulionic acid. ionic acid. aiiylpyrimidine.

nine. 50 d0 1,2-dich10r0-4-11itr0- 7 1 d0 7 3 2,4,6-trichioro-5-car- 7 1 Do.

benzene-G-sulfonic bomcthoxypyrimacid. i e. 51 Tetra-3-mercapto d0 1 d0 3 2,4,6-tr ibromo-5- 1 Do.

copper phthalocysr bromovinylpyrimi- N (2 111 :11 1) I ding" 4 -c oroe y 1 52 do ethyiamine. 5 175 D 3-br0m0-2-hydrorry-pr0- 2 5 me ypynml' 7 2 (Dane1-]1-fuli0ni():ac1i1d. met yamino -et yi- 7 s3 d0 l-suifonic acid. 1 3 D 7 2-chiorocthar1c-1-sui- 2 7 me g ny 7 ionic acid. pymm 54 do 1-ch1oro-2,4di-nitro 1 3-ch10ro-2-hydroxy-pro 3 7 do 1 Do. be ilzene-fi-suiionic pane-l-suiionic-acid.

acr 55 do do 1 d0 3 2,4,6-trichior0-5- 1 Do.

. chioromcthyl- 7 pyrimidine. 56 do 1-c111or0-4-nitro-bcn- -1 do 3' 2,4,6-trichloro-5- 1 D zeneQ-sulionic acid. carboethoxy- 1 D0.

pyrimidine.

57 d0 1 d0 3 7 2,4,6-tirbrom0-5- 1. Do. mcthylpyrimidine. 58 Tetra 3-mercapto do 2 2-ch10r0ethane-1-sul- 2 2,4,5,6-tetrach1oropy- 1. 2 D0.

phthaiocyaninc. ionic acid. rimidine. 7 59 d0 d0 1. 5 d0 2. 5 2,4,6-tribr0mo-4- 1. 5 Do, 7 1 carboxymethyipyriniidinc.

EX. Polymercapto- Shade of pad N o. phthalocyanine Phenylating agent(s) Moles Alkylating agent(s) Moles Reactive system Moles dyeitng on co ton 2-ehloroethane-1-sulr 60 Tetra-3-mercapto ionic acid. 2 gfi'g 1 Green.

phthalocyanine. Z-chloro-ethylamine. m 61 do 1,2-dichloro-4-nitro- 2 3-ehloro-2-hydroxypro- 2 do 2 D0.

berilzene-o-sulfonie pane-i-sullonic acid. 2 act 62---- Tetra-3-mereapto d 2 --d0 2 2,4,5-tribromopyrimi- 1 D0.

copper phthalocyadine. nine. 63 do l-chloro-i-nitro-beu- 2 -do 2 2,4,6-triehloro-5-a1lyl- 1 Do.

zene-2-sul1onic acid. pyrimidine. 64".-- Tetra-'4-mercapto -do 2 do 2 2, 4, 6-tribromo-5- 1 Do.

copper phthaearboethoxylocyanine. pyrimidine.

2-eh10roethylamine. 1 }2, 4, G-triehloro- 1 Do 1 2-ehloro-ethane-l- 2 pyrimidine.

sult'onic acid. 2 2-ehloro-ethane-l- 2 2, 5, 6-tribromo-4- 1 Do.

sulionio acid methylpyrimidine l-gigdinobutyl-ii-sulfuric 1.2 2, 4, 6 mchlom 1 2 Do 1 G7 2-eh1oroetha-ne-l- 2. 8 pymmdme' sulfonic acid.

1 In Examples 7 and 8 the two nitro groups of the phenylat-ing agent are reduced to amino groups after the formation of the phenyl and of the alkyl thioether; one amino group is then reacted with the reactive system, whereas the three other remain free.

In Example 54 after the phenylation and alkylation of the thiol groups one of the two nitro groups of the phenylating agent is reduced to an amino group which is reacted with the 2, 4-dichloro5-ch1oromethyl-fi-methylpyrimidine, whereas the other nitro group remains free.

3 In Example 55 the two nitro groups of the phenylating agent are reduced to amino groups after the formation of the phenyl and of the Alkyl thioether; one amino group is reacted with the 2, 4, G-triehloromethy1-5-eh1oromethylpyrimidine and the other remains free.

4 In Example 65 the nitro group of the phenylating agent is not reduced.

Formulae of representative dyes of the foregoing examples are as follows.

Example 1 (last paragraph):

Example 1:

(HI OH SCH2CHCH2SO3H S-OHz( 3HOH2-SOaH v p 7 0H 40 s-cHioH oHt-s0u1 I SCH:( 3HCH2SO3H SOKH l/ S|O3H NiPC(3)\-iONHz 11 (3 Cu Poo s 3 NHE ([31 803E O I f 303E f SNH0 -o1 SGNHJ to. C]

NiPC denotes the nickel ph-thalocyanine radical. Example 2: CuPC represents the copper phthalocyanine radical; 0H (3) denotes that the four SP-- are bound to the copper I phthalocyanine radical in the four 3-positions. SOH2CHCHzSOaH Example 1 (penultimate paragraph): OH

SCH2|CH-UH2SO3H SOaH S CH2 OHZ-SO3H Cl1-PC(3 s NH2 SCH2CH2SO3H 5 I I 7. $0313 01 $0311 0 I l N N O ou-Po 3)s NH2 o1 -NH I It 0 803E or o s fi 1'1 s NHC 0-01 1 mixture of the 2,6-dichloropyrirnidyl-4 dyestufi and 4,6-

dichloropyrimidyl-Z-dyestuif.

Example 3:

on S-CH2C HCHnSOaH (4) denotes that the four S are bound to the 'copper phthalocyanine radical in the four 4-positions.

Ca al/agile chloromethylpyrimidine and 2,4 di chloro 5 chloromethyl-6-methylpyrirnidine (cf. formula of Examples 5 and 32).

Having thus disclosed the invention what I claim is: 1. Dyes of the formula wherein PC is the radical of a member selected from the group consisting of an unsubstituted Inetalfree phthalocyanine, an unsubstituted metal-containing phtheilocyanine, a metal-containing phthalocyanine bearing one to 2 chlorine atoms and a V metal-containing phthalocyanine bearing one to 2 bromine atoms, metal having an atomic number from 28 and 29,

A is a member selected from the group consisting of low molecular'alkylene and'low molecular hydroxyalkylene,

each of A and A3 is a member selected from the group consisting of phenylene, chlorophenylene, nitrophenylene, aminophenylene, low molecular alkylene and low molecular hydroxyalkylene,

R is a member selected from the group consisting of dihalogenopyrimidyl and trihalogenopyrimidyl, halogen having an atomic Weight between 35 and 81,

R is a member selected firom the group consisting of hydrogen and loW molecular alkyl,

n possesses a value of at least 2"but not more than 4 in the absence of phenylene radicals and at least 3 but not more than 4 in the presence of a phenylene radical and m, x, y and z each possesses a value of at least 1 but not more than 4, the total x+y+z being 6 and the SO H and groups being attached to the radicals A A and 3. 2. The dye of the formula 13 14 4. The dye of the formula 6. The dye of the formula OH SCH2-(JHCH2SO3H B 5 w S-C Hr- C H-CH2SO:H s c HPCH CH2 S 0 3H 0H SOaH 1 S-CHr-CH-OHa-SOaH Cu-PO a s NH C1 O Cu-PG(3 SCH2CH2NH2 I I c 1 50311 0 l s H N/ N m SCH:-OH2-NH-O\ J=C1 N 41 7. The dye of the formula s-om-cm-som 5. The dye of the formula s-cHg-cHg-soaH OuPO(3)-S NH:

SCHnCHaSO;H 01

803E S0311 I O-N I SGNH CH 0 0 01 NiPC(3 SONH2 o1 V I c= SOzH %C\ (13H:

| N N C1 References Cited in the file of this patent (I: FOREIGN PATENTS 01 805,562 Great Britain Dec. 10,1958 

1. DYES OF THE FORMULA
 2. THE DYE OF THE FORMULA 